Preparation of substituted indenes



Oct. 5, 1965 w, REDDIE ETAL 3,210,443

PROCESS FOR PRODUCING POLYESTER PLASTIC SPHERES Filed NOV. 14, 1963 WILLIAM A, REDDIE GERALD D. OGDEN THOMAS E. SAMPLE JR.

INVENTOR.

w P M Qz/i y United States Patent Ofice 3,210,443 Patented on. s. was

3,2l0,443 PROCESS FOR PRODUCING POLYESTER PLASTIC SPHERES William A. Reddie and Gerald D. Ogden, Houston, and

Thomas E. Sam le, In, Austin, Tex asslmiors to Magnet Cove Ba m Corporation, a corporation of Arkansas Filed Nov. 14, 1963, Ser. No. 323,644 12 Claims. (Cl. 264-14) This invention relates to the art of producing small solid spheres of plastic materials. It is particularly directed to a process for producing substantially perfect spheres of thermoset polyester plastics.

Small plastic spheres of equal size have a great many uses as, for example, in insulation where the relatively large body of quiescent air trapped between small spheres of uniform size effectively minimizes heat transfer through the mass, and such balls have been suggested as frictionreducing hearings in applications where the load is not too great. Another common use is as fracture propping agents in fracturing underground formations adjacent to oil or gas wells to increase the production of petroleum materials.

In the fracturing process, a fluid is pumped into a well bore penetrating a producing formation under very high pressure so that the fluid from the well flows into the sandstone of the formation and splits or cracks the formation in a manner to increase the exposed surface from which the oil or gas is produced. A propping agent is disposed in the fracture while it is open to prevent the fracture from closing when the high pressure is released.

Plastic balls made of styrene-divinylhenzene cross'linlted resin manufactured by a suspension polymerization" process have been suggested as fracture propping agents and these materials are satisfactory in most cases. Resins of thermosetting type however have been made into spherical form in the past entirely by suspension polymerization. This process, as is shown in US. Patents 2,6l0,l70, 2,610,171 and 2,652,386, comprises dispersing a liquid thermosetting prepolymer in a liquid heat-transfer medium maintained at a temperature sufficiently high to cure the pro-plastic material, and maintaining the pro-plastic material in suspension by agitation and rapid circulation of the hot heat-transfer medium to prevent settling of the preplastic until the desired degree of polymerization is attained.

This process results in the formation of droplets of liquid pre-plastic of a wide range of sizes in the liquid heat-tranfer agent. During the time the droplets are suspended for curing, which may be five minutes or more, the degree of agitation necessary to keep the droplets in suspension causes some of the droplets to be broken up into still finer ones, and results in other suspended droplets coming into contact with each other and coalescing to form larger ones. The size of the cured plastic spheres varies so greatly from sphere to sphere that it is impractical to produce spheres that are substantially uniform in size. It is customary to screen out spheres that are within a desired size range, such as 20 to 40 mesh and to use a product of such mixed sizes. US. Patent 3,089,542 teaches the use of spheres of different diameters within a selected size range as propping agents in fracturing formations tor the production of oil and gas. Spheres of substantially uniform size will form a bed having a greater volume of voids and hence more permeable than a bed formed from spheres of mixed sizes.

A large proportion of undersize and oversize particles outside of a desired size range are produced by the suspension polymerization process, together with spheres of ditferent diameters within the desired size range; and on screening out the undersize and oversiu particles there is a considerable waste of material.

It is an object of the present invention to provide a process for the production of substantially perfect, solid spheres of thermoset polyester plastic in which the spheres are substantially uniform in size and waste due to production of undersiu and oversize particles is minimized.

Another object is to provide a process of the above type in which spheres of a liquid thermosetting preplastic are initially set and cured while drifting slowly downward through a substantially quiescent liquid heat-transfer medium.

Another obiect is to provide such process in which contact of the spheres with each other or with apparatus, v. hile in soft or sticky condition, is avoided.

Another object is to provide a process of the above type which results in strong, resilient spheres unaffected by salt water and oil and suitable for use as fracture propping agents.

Other objects, advantages and features of this invention will be apparent to one skilled in the art upon a consideration of the written specification, the attached claims and the annexed drawing.

The term "polyester pre-plastic" is used in this specification and claims to mean a solution or suspension of an unsaturated polyester of a dihydric alcohol and dibasic organic acid in a monomer having a vinyl linkage reactive with the polyester at elevated temperatures to form a thermoset plastic. Unsaturation is introduced into the polyester by use of an unsaturated dibasie organic acid in its preparation as, for example, fumaric acid, maleic or phthalic acids or their anhydrides, or mixtures thereof. A minor amount of a saturated dibasic acid, such as adipic acid, often is included in the acid mixture. Ethylene glycol, diethylene glycol, propylene glycol, or the like, or a mixture thereof, usually is used as the dihydric alcohol. These polyesters are known to be of linear structure with recurring double bonds.

It is common commercial practice to carry out the, polyesterifieation reaction with substantially stoichiometric' proportions of dibasic acids and dihydric alcohols and to continue the reaction until the product has an acid number in the range from about 10 to 50. The resulting polyester resin usually is solid but is soluble or suspendable in a monomer having a vinyl linkage. Styrene, vinyl toluene, divinylbenzene, methylstyrene, methylmethacrylate, and diallyl phthalate are the most commonly used monomers. The monomer is usually present in the polyester pre-plastic to an extent of about 20 to 50 percent by weight.

Since such polyester pro-plastics are common articles of commerce and are readily available from a large number of manufacturers and the present invention is not limited to any particular polyester pro-plastic, it is not believed necessary to describe the starting materials in greater detail.

In the present process substantially uniform spheroidal drops of a tree'howiug liquid polyester are-plants are extruded front a nozzle. preferably a nestle havlns multiple uniform orifices laterally spaced from each other to fall downward through a gas. preferably air, into a body of a hot liquid inert to and immiscible with the drops and having high heat-transfer characteristics.

The size of the orifice or multiple uniform orifices is selected so that the extruded spheroidal drops are untform in size and have a volume substantially equivalent to a sphere having a selected diameter in the range from 0.09 to 0.25 inch. Commercial hypodermic needles cut oil at a right angle to their axes may be used as dropping orifices if desired and have been found to result in drops of the following average sizes, according to needle gauge.

Average diameter It is preferred that the free-flowing, pie-plastic mixture be extruded at a rate of about one drop per second from each orifice to secure best uniformity in size.

The distance that the spheroidal drops fall freely through the gas is selected so that it provides time for the drops to acquire substantially spherical shape before contact with the hot heat-transfer liquid, and insufl'icienf for the drops to acquire sumcient velocity to break them up into finer particles by impact upon the surface of the liquid. This distance will usually be in the range from one to four feet. The liquid heat-transfer medium is maintained at sniliciently elevated temperature to cure the polyester preplastic material in the drops. it is not necessary that the temperature be uniform throughout, in fact convenience in heating is best obtrained by maintaining a heat gradient between top and bottom of the liquid. Temperatures within this gradient are maintained below the boiling point of the lowest boiling material in the particular polyester pre-plastic used and above the melting point of the highest melting material therein. It is preferred that this gradient be entirely within the range from about 200 F. to about 300" F., since temperatures below 200 F. increase the time required for initial cure and top temperatures above 300 F. are unnecessary, even when such high boiling monomere as divinyl benzene or diallyl phthalate are used.

The liquid heat-transfer medium is selected so that it not only has high heat-transfer properties but is inert toward the falling drops and is immiscible therewith. After contact with the hot liquid heat-transfer medium, the drops are passed slowly downward by gavity through the liquid heat-transfer medium in free-falling relationship therewith, for a time suflicient for initial cure of the polyester pro-plastic. and cure of the spherical drops preferably is completed in a lower part of the heat-transfer medium although the initially cured spheres may be withdrawn from the liquid heat-transfer medium and ouring completed elsewhere, if desired.

The commercial polyester pre-plastics available on the market often are too viscous for extrusion of the material in drops of the required size at practical rates, and in this case we prefer to dilute the pro-plastic material with additional monomer. The monomer used for dilution to form a free-flowing liquid may be the same monomer which is present in the commercial polyester pro-plastic or any of the other elfective monomers may be used for dilution purposes. Styrene is a preferred monomer for dilution when cheapness is the principal characteristic required in the final product, and diallyl phthalate is preferred when highest strength is required. Any of the other monomers mentioned above may be used or mixtures thereof; but in any case when viscosity of the commercial material is too high, sutllclent monomer is mixed with the commercial polyester ore-plastic to convert it to a treedlowing liquid.

A curing catalyst. such as benzyl chloride. aniline hydrochloride. hydroxylammonium acid sulfate or benaoyl peroxide. should also be mixed with the tree-flowing polyester pre'plastic in quantity sufficient to substantially increase the rate at which the mixture reacts at a given temperature. Benzoyl peroxide is the preferred catalyst for this use. Benzoyl peroxide is sold commercially in the form of a paste containing 50 percent active ma terial, and this commercial paste gives good result when mixed with the polyester pre'plastic. This 50 percent paste of benzoyl peroxide in tricresylphosphate may be mixed with the pro-polymer in proportions in the range from 2 to it percent by weight, or preferably about 4 percent, thus supplying a benzoyl peroxide content in the pre-plastic material of from i to 4 percent, with the preferred content being about 2 percent.

The liquid beat-transfer medium may be any liquid which is inert toward the pro-polymer and immiscible therewith and which has high heat-transfer characteristics accompanied by specific gravity and viscosity such that the drops pass slowly downward through the heattransfer medium.

It is desirable that the liquid heat-transfer medium have a high flash point, high boiling point, low vapor pressure and have no adverse chemical reactivity with the pro-plastic during the cure. It is further preferred that the heat-transfer medium be non-toxic, non-flammable and non-foaming. The viscosity of this medium is preferably in the range between 5 and 30 cps. at F. The medium preferably should be transparent or translucent so that falling drops can be observed by an operator as they drift slowly down through the heattransfer medium and it must have a density less than the density of the cured polyester plastic.

One preferred liquid heat-transfer medium is a mixture of ethylene glycol and glycerol in proportions in the range from 3 to 5 parts by volume of ethylene glycol to 1 part of glycerol. Mixtures of this type are preferred because they have the required properties set forth above as desirable in a liquid heat-transfer medium and have the proper relationship of specific gravity to specific gravity of the extruded drops. Proportions outside these ranges of ethylene glycol to glycerol may be used in the rare cases where the specific gravity of the cured spheres is less than that of the mixtures in the proportrons stated above. The particular mixtures in which ethylene glycol is in the range from 3 to 5 parts by volume to 1 part of glycerol have specific gravities in the range from about 1.137 to about 1.141, at room temperature.

We have also found that a mineral oil liquid heattransfer agent containing about 3 percent of a colloidal dispersion of a reaction product of dirnethyldioctadccylammonium halide and a magnesium montmorillonite is an excellent liquid heat-transfer medium although it has a specific gravity of about 0.85 at 200 F. depending upon the specific gravity of the oil prior to the addition of the clay compound and the exact quantity of clay compound added. Other viscosity-increasing materials also may be blended with mineral oil in order to raise the viscosity thereof and the resulting mixtures used as heat-transfer media. The organophyllic clay complexes made by reacting a long allryl chain quaternary ammonium halide with a clay are preferred viscosity-increasing materials when mineral oil is used. Although there is a large diftcrerice between the specific gravities of the oil mixture and the extruded drops, the drops will drift slowly downword through the medium at the preferred rate of travel due to the high viscosity of these mixtures. A viscosity of about l2 to l6 cps. is preferred.

The rate of travel of a particular size drop downward through the liquid heat'transfer medium may be com trolled either by selecting a heat'tt'attttict medium having a specific gravity in such relationship with the specific gravity of the drops that the proper rate of travel is obtained. or by selecting a viscosity for the heat-transfer medium such that the drops pass downward therethrough at a slow rate. It is preferred that the rate of travel of the drops downward through the heat-transfer medium require about 2% to l seconds per linear foot of travel.

The depth of the body of liquid heat-transfer medium is selected so that the drops will move slowly downward through the substantially quiescent medium without contact with each other or with any apparatus used until initial cure has occurred and the spheres are no longer in soft and sticky condition. The time required for initial cure is about 20 to 40 seconds. Since additional curing during passing of the drops downward through the liquid is not deleterious, it is preferred that the depth of the body of liquid heat-transfer media be selected in the range from about 10 to 20 feet than in the range from 2 to to feet required to provide travel time for initial cure at the above rates of descent.

A body of liquid heat-transfer medium of this depth provides suflicient volume in the bottom thereof for retaining initially cured spheres for a time sufiicient to complete the cure. We have found that spheres of the sizes described are completely cured in a time in the range from to minutes. Cured in this manner, the spheres are clear and free from cracks, checks or internal strains which substantially reduce their compressive strength. i

The liquid heat-transfer medium is maintained at temperatures below the boiling point of the lowest boiling material, usually the monomer, in the polyester pro-plastic therein, preferably temperatures in the range from about 200" F. to 300" F., preferably 200 F. to 275 F. Normally there will be a heat gradient between the top and bottom of the body of heat-transfer media, and this range will include a bottom temperature in the neighborhood of 200" F. and a top temperature in the range from 225 F. to 300 F. We have found that, if the top temperature is less than 225 F., the extruded drops falling upon the surface of the liquid tend to be badly deformed and are broken by impact and an excess amount of fine material is famed. We have found that best results in elimination of line material is usually attained at about 245 F. and a top temperature near this value is preferred, accompanied by a bottom temperature of about 210" F.

It is preferred that the spheres be retained in the bottom of the heat transfer media until complete cure is accomplished. This, however, is not necessary; but after the initial cure, the spheres are in sufliciently hardened condition that they will not be deformed by careful handling; and, if desired, they can be withdrawn and the cure completed in auxiliary apparatus. However, this complicates the process and ordinarily is not advantageous and so is a less preferred procedure.

After curing the spheres may be washed free of any excess liquid heat-transfer medium, are dried and are ready for use. When ethylene glycol-glycerol is used as the heat-transfer medium, the spheres may be washed with water; or when a mineral oil thickened with a hydrophyllic clay complex is used, a solvent such as acetone is used for washing. By proper control of the critical variables set forth above, a yield of closely sized substantially spherical pellets amounting to more than 95% of the weight of resin consumed may be obtained.

The attached drawing illustrates diagrammatically one system of apparatus which may be used in carrying out the process of this invention. In the single figure, the reference numeral 1 designates a mixing tank into which a commercial polyester pre-polymer is introduced from a source (not shown) through line 2 and a monomer Ill such or styrene or diallyl phthalate, it required. is introduced throueh line 3 in quantity sutlicient to dilute a viscous polyester ore-plastic to convert it into a freeflowiog liquid. Tank I preferably is equipped with a motor driven agitator 4. llenzoyl peroxide in the range from about 1 to 4 percent of the total polyester preplastic mixture is supplied byline 5. and the ingredients introduced into tank I are thoroughly mixed by operation of the agitator 4.

An inert gas, such as nitrogen. under pressure in the range from about 3 to 15 p.s.i.g. is introduced from a source (not shown) at 6 so that pressure upon the surface of the liquid in tank 1 is maintained without unneces sary exposure to oxygen from the air which might tend to cause curing to begin while the mixture is still in tank 1.

The thinned polyester pro-plastic is passed under pressure from the inert gas in tank 1 through line 7, having a valve 0, into extrusion head 9, and preferably having a plurality of uniform orifices illustrated as provided by cut-off hypodermic needles It. The orifices 11 are of uniform size and the rate of flow of the polyester preplastlc is controlled so that spheroidal drops of this matel-lat are extruded from each of the orifices 11 at a rate of about I drop per second.

The extruded drops 12 then fr." freely through gas. preferably air, for a distance sufficient for them to acquire substantially spherical form and preferably 2:. the range from about 1 to 4 feet. The falling drops 12 fall into a liquid heat transfer medium in a vertical column designated generally as 14. This liquid heat transfer medium is preferably a material selected from the group consisting of mixtures of ethylene glycol and glycerol, and mixtures of mineral oil and a reaction product of a long alkyl chain quaternary ammonium halide and a clay. The liquid heat-transfer medium is maintained at tem peratures in the range from 200' F. to 300 F. by any suitable heating means, illustrated as a steam jacket 15, so there is a heat gradient in the substantially quiescent liquid 13 from a cooler temperature at the bottom of column 14 to a temperature in the range from 225 F. to 300 F. at the upper surface of liquid 13; and preferably the upper part of liquid 13 is maintained at a temperature of about 245' F.

The drops 12 fall upon the surface of liquid 13 and sink slowly downward theretltrough at a rate of about 2% to 10 seconds per foot of linear travel determined by the viscosity and specific gravity of liquid 13. The height of column 14 is selected to provide sufficient distance for the drops to sink slowly through liquid 13 at this rate for a time in the range from about 20 to 40 seconds or more. During their passage downward through the heat-transfer medium, the droplets complete their initial cure and the resulting spheres of polyester plastic accumulate in the lower part of column 14 and are there retained for willcient time to complete their cure. The total curing time required is ordinarily in the range from S to 10 minutes.

After the spheres have been completely cured, they are withdrawn from column 14 valve 17 and are passed to a centrifuge 18 where liquid heat-transfer medium withdrawn with the spheres is separatd from them. The spheres are then passed as indicated by the arrow 19 to any suitable washing and drying steps desired. The separated liquid heat-transfer mdium is then withdrawn by line 21 and pump 22 and passed through a filter 23 to remove any detritus that may have been formed. The filtered heat-transfer medium is then passed to a heater 24 and is recycled through line 25 to an upper part of column 14.

The following examples illustrate the results obtained in forming substantially perfect polyester plastic spheres from readily available commercial polyester pro-plastic to materials.

by line 16 containing 1 mime r A little number at commercially available polyester pre-ptastle materials were tormed into spheres by the following procedure.

A mixture benmyl peroxide and the polyester preplastic was prepared by adding benzoyl peroxide paste in quantities ranging lrom 2 to 8 percent of the commercial polyester pre-plastic material, diluted with monomer it required and mixing thoroughly w'th a Hamilton Beach mixer. After the peroxide paste was thoroughly dispersed in the resin, the mixture was introduced into a dropping head having a plurality of uniform orifices formed from cut-oft hypodermic needles. Gas pressure in the range from 3 to 15 p.s.i.g. was applied to the mixture with the result that drops were extruded from each of the orillces at an approximate rate of 1 drop per second. The gas used as pressure medium was nitrogen.

The drops then fell through air into a column of hot heat-transfer liquid where they were cured. The distance from the dropping head to the surface of the heattransfer liquid was selected so that it provided a falling time in air suflicient tor the spheroidal extruded drops to become substantially spherical. The selection was made by moving the dropping head vertically up and down to a distance required by the particular polyester pro-plastic material being tested. This distance was found to vary according to the composition of the polyester pre-plastic but was in the range from t to 4 feet. It was found that too great a distance resulted in the drops acquiring sull'icient velocity that they became deformed or shattered on impact with the surface of the heat-transfer medium.

The heat-transfer liquid used in this series of tests was a mixture of ethylene glycol and glycerol having its specific gravity adjusted to a value slightly below the spcific gravity of the extruded dro For increasing the specific gravity when necessaly, additional glycerol was added to the mixture; and when it was necessary to decrease the specific gravity, a larger quantity of ethylene glycol was blended into the mixture.

The drops were passed slowly downward to provide time for initial cure before the drops came to rest at the bottom of the column of heat-transfer liquid. Initial cure was such that the drops were no longer in soft and sticky condition, and had sutlicient rigidity that they were not deformed by weight of overlying drops when a pile of initially cured drops accumulated in the lower part of the column. It was found that a falling time through the heat-transfer liquid in the range from about 20 to 40 seconds was sutltcient for such initial cure and that the time required varied somewhat with the composition of the polyester pro-plastic.

After the spheres reached the bottom of the column of heat-transfer liquid, they were held for additional time to provide a total of 5 to minutes for complete cure.

The heat-transfer liquid was heated by winding a Pyrex glass tube in which the liquid was contained with oneinch electric heating tape. it was found that the tube easily transmitted heat to the liquid contained therein at a rate sufllcient to maintain the liquid in the range irom 200 F. to 300' F. It was found that a temperature of the heat-transfer liquid at the surface thereof when maintained at about 245' P. resulted in maximum decrease in the number of falling drops shattered or broken up by impact with the surface of the liquid. At'ter complete cure, the spheres were removed from the heat-transfer medium and washed with water and dried.

The dried spheres were subjected to compressive strength tests and were examined for freedom from cheeks, cracks and internal strains. All were substantially clear and free from internal strains, checks and cracks and had good compressive strength at room temperature. the materials tested and the compressive strength of spheres having an average diameter of 0.1304 inch were as follows:

vAntout-t'ucaa't'w means Com all" 5 Error: th 0! Polyester Pro-Plastic Maoutacturer Inrllv duel head at Room 'lem- [mature Pounds) Alpha Chemical Platehhbld Chflmlttfll... tlpha Chemical 350 *ltlelml'lh Plate Glass" 215 l 800 160 185 its 860 285 Nangatuck Chemical 205 }Alphn Clusmleal..-.. 150 till Alteh t Alpha Chemical 2m l Iolyllm llU-d'l' Kalchhotd Chemlcnl. 5% iii? i112: i Chemise mo 1 rowan; nu-aaz Reichhold Chemlcal- Table I COMPARISON or vuvarr-sr. onutmranmrws or EXAMPLE I! The experimental work described in Example I was repeated, using a mineral oil containing about 3 percent of a colloidal dispersion of a reaction product of dimethyldioctadccylammonium halide and a magnesium montmon'li nitc widely sold under the name Bcntone 38 as the liquid heat-transfer agent. This heat-transfer medium had a specific gravity of about 0.85 at 200' F. and a viscosity of 44 centipoises. There were no other difierenccs in procedure from that of Example 1 other than that the beads were washed with acetone rather than with water after the final curing. Tests of compressive loads at room temperature and at 200 F. on individual spheres having an average diameter of 0.1304 inch were made. The best results were given by the following polyester pre-plastic materials.

Table 2 COMPARISON OF PHYSICAL CHARACTERISTICS OF VARIOUS PLASTIC BEADS Comaatlvo Polyester Pro-Plastic Manulocturer Room 1 cmrnturo ounda) vlhrtn roan Nnugatuclr Chemlcal.. P420 Alpha Chornical.-. 3 Pittsburgh Plate Gloss 2Z5 lnterchemlcal 320 Compressive Load at 200 F. (Pounds) lnberchemlonl 1 lnterehernteal a: Rulchholti Chemical 155 lntcrchcmlcal EXAMPLE Ill In order to compare the strength of polyester spheres prepared in the two types of liquid heat-transfer media, the following tests were run. The procedure was the same as in Example 1 except that the mixture or polyester pro-plastic was cured in the ethylene glycol-glycerol mixture described above, and the same experiment was repeated using the same material cured in the mineral oil containing about 3 percent of the reaction product of dimethyldioctadecyl ammonium halide with a magnesium montmorillonite, widely sold under the name "Bentone 38." The following results were obtained:

Tobie 3 OOIIPABIBON r TWD CURING MEDIA i Q am 4 Alllfl Pa m,

at its a... in .u. up,

uiiifurii'ffi'ffi'f'. am 0.09! 0.1m Uom ve Strength It ylcno fllyool (Room 1 our lso; ten I00 Compress treng i'ilifilflffilffiflffi... us or 12s The differences in strength found were without significanoe.

From the foregoing it will be seen that this invention is one well adapted to attain all ofthe ends and objects hereinahove set forth, together with other advantages which are obvious and which are inherent to the process.

It will be understood that certain features and subcomblnations are of utility and may be employed wlthout reference to other features and suboombinations. lhrs is contemplated by and is within the scope of the clauns.

As many possible embodiments may be made of th e invention without departing from the scope thereof, it rs to be understood that all matter herein set forth or shown in the accompanying drawing is to be interpreted as illustrative and not in a limiting sense.

The invention having been described, what is claimed is:

l. A process for producing spheres of thermoset polyester plastic comprising mixing a catalyst with a liquid polyester pro-plastic; extruding the resulting mixture tn uniform spheroidal drops, each substantially equivalent in volume to a sphere having a diameter in the range from 0.09 to 0.25 inch; dropping the extruded drops freely downward through a gas into a substantially quiescent, hot liquid heat-transfer medium inert to the drops and immiscible therewith through a distance suflicient for the falling drops to acquire substantially spherical shape and insuilicient for the drops to acquire sullicient velocity to break up the drops on contact with the hot liquid heattransfer medium; maintaining the temperature of the liquid heat-transfer medium below the boiling point of the lowest boiling material in the drops and above the melting point of the highest melting material therein; passing the drops slowly downward by gravity through the heat-transfer medium for a time sufficient for initial cure of polyester plastic; and completing cure of the resulting spherical drops in a lower part of the heat-transfer medium.

2. A process for producing spheres of thermoset polyester plastic comprising mixing bcnzoyl peroxide with a liquid polyester pro-plastic; extruding the resulting mixture in uniform spheroidal drops at a plurality of laterally spaced locations, said drops having volume substantially equivalent to that of a sphere having a diameter in the range from 0.09 to 0.25 inch, and being extruded at a rate of about one drop per second at each location; dropping the extruded drops freely downward through a gas into a substantially quiescent, hot liquid heat-transfer medium inert toward the drops and immiscible therewith through a distance sufficient for the falling drops to acquire substantially spherical shape and insufficient for the drops to acquire sufficient velocity to break up the drops on contact with the hot liquid heat-transfer medium; maintaining the temperature of the liquid heat-transfor medium below the boiling point of the lowest boiling material in the drops and above the melting point of the highest melting material therein; passing the drops slowly downward by gravity through the heat-transfer medium in free-falling relationship therewith for a time suflicient for initial cure of polyester pro-plastic; and completing cure of the resulting spherical drops in a lower part of the heat-transfer medium.

3. A process for producing spheres of thermoset polyt0 crlcr laulc comprising mixing from I. to 4 weight percent 5! bcmyl rcroxldc with a liquid pol proteller plastic: extruding the resulting liquid mixture in uniform spheroidal drop: substantially gluten! to volume to a ipherc havina a diameter in 2 range from 0.09 to 0.25 inch at each of a plurality of laterally spaced localions at a rate of about one drop per second at each location; dropping the extruded drops freely downward through air for a distance of about I to 4 feet into a hot liquid heat-transfer medium inert thereto and immiscible therewith. said heat-transfer medium having specific gravity and viscosity such that the drops fall freely theretbrough at a rate of about-2% to 10 seconds per linear foot of travel; maintaining the temperature of the liquid heat transfer medium in the range from about 200' F. to 300' F.; and completing cure of the spherical drops in a lower part of the heat-transfer medium.

4. A process for producing spheres of thermoset polyester plastic comprising thinning a viscous polyester preplastic with sufficient monomer to produce a free-flowing liquid; mixing from I to 4 percent of benzoyl peroxide with the liquid polyester pro-plastic; extruding the resulting liquid mixture in uniform spheroidal drops substantially equivalent in volume to a sphere having a diameter in the range from 0.09 to 0.25 inch at each of a plurality of laterally spaced locations at a rate of about one drop per second at each location; dropping the extruded drops freely downward through air for a distance of about 1 to 4 feet into a hot liquid heat-transfer medium inert thereto and immiscible therewith and having a specific gravity in the range from about 1.137 to L141; maintain ing the temperature of the liquid heat-transfer medium in the range from 200' F. at the bottom of the body of liquid to not more than 300 F. at the top of the heattransfer medium; passing the drops slowly downward by gravity through the heat-transfer medium in free-folk ing relationship therewith at a linear speed of about 2% to 10 seconds per foot for a time in the range from about 20 to 40 seconds; completing cure of the spherical drops in a lower part of the heat-transfer medium; and separating the resulting spheres of thermoset polyester plastic from the heat-transfer medium.

5. The process of claim 4 wherein cure of the spherical drops in the lower part of the heabtransfer medium is continued for a time sufficient to provide a total curing time of about 5 to ID minutes.

6. The process of claim 4 wherein the heat-transfer medium is a mixture of ethylene glycol and glycerol in proportions from 5:1 to 3: l.

7. The process of claim 4 in which benzoyl peroxide is used at about 2 percent of the weight of polyester preplastic.

8. The process of claim 4 wherein the beat gradient is from 200 F. at bottom to a temperature in the range from 225' F. to 300 F. at top.

9. The process of claim 4 wherein the heat transfer medium is maintained in a temperature gradient tom about 200" F. at the bottom thereof to 275 F. at the top.

10. The process of claim 4 wherein the heat gradient is from about 210' F. at the bottom to about 245' "F. at the top.

11. A process for producing spheres of thcrmoset polyester plastic comprising thinning a viscous polyester preplastic with sufficient monomer to produce a free-flowing liquid; mixing from I to 4 percent of benzoyl peroxide with the liquid polyester pro-plastic; extruding the resulting liquid mixture in uniform spheroidal droplets substantially equivalent in volume to a sphere having a selected diameter in the range from 0.09 to 0.25 inch at each of a plurality of laterally spaced locations at a rate of about one drop per second at each location; dropping the extruded drops freely downward through air for a distance of about one to four feet into a hot liquid heattrausfer medium consisting essentially of a petroleum oil thickened with a reaction product of a long chain alkyl quaternary ammonium halide and a clay; maintaining the temperature of the liquid heat transfer medium in the range from 20 F. at the bottom of the body of liquid to not more than 300' F. at the top at said body of liquid heut'transfer medium: posting the drops slowly down ward by gravity through the heat-transfer medium in free-falling relationship therewith at a linear speed of about 2% to 10 seconds per foot for a time in the range from about 20 to 40 seconds; completing cure of the resulting spherical drops in a lower part of the body of liquid heat-transfer medium; and separating the resulting spheres of cured thermoset polyester plastic from the heaHransfet medium.

12 The process of clgtirn ll wherein the reaction with net is the prequel of dtmethyldioctarleeylammonium ha lrde reacted Wtlh magnesium montmorillonite.

Rehreum Cited by the Emil" UNITED STATES PATENTS 2,087,0l9 7/37 Clement 264-13 2,652,386 9/53 Wallman 264* l ALEXANDER H. BRODMERKEL, Primary Examiner.

ROBERT F. WHITE, Examiner. 

1. A PROCESS FOR PRODUCING SPHERES OF THERMOSET POLYESTER PLASTIC COMPRISING MIXING A CATALYST WITH A LIQUID POLYESTER PRE-PLASTIC; EXTRUDING THE RESULTING MIXTURE IN UNIFORM SPHEROIDAL DROPS, EACH SUBSTANTIALLY EQUIVALENT IN VOLUME TO A SPHERE HAVING A DIAMETER IN THE RANGE FROM 0.09 TO 0.25 INCH; DROPPING THE EXTRUDED DROPS FREELY DOWNWARD THROUGH A GAS INTO A SUBSTANTIALLY QUIESCENT, HOT LIQUID HEAT-TRANSFER MEDIUM INERT TO THE DROPS AND IMMISCIBLE THEREWITH THROUGH A DISTANCE SUFFICIENT FOR THE FALLING DROPS TO ACQUIRE SUBSTANTIALLY SPHERICAL SHAPE AND INSUFFICIENT FOR THE DROPS TO ACQUIRE SUFFICIENT VELOCITY TO BREAK UP THE DROPS ON CONTACT WITH THE HOT LIQUID HEATTRANSFER MEDIUM; MAINTAINING THE TEMPERATURE OF THE LIQUID HEAT-TRANSFER MEDIUM BELOW THE BOILING POINT OF THE LOWEST BOILING MATERIAL IN THE DROPS AND ABOVE THE MELTING POINT OF THE HIGHEST MELTING MATERIAL THEREIN; PASSING THE DROPS SLOWLY DOWNWARD BY GRAVITY THROUGH THE HEAT-TRANSFER MEDIUM FOR A TIME SUFFICIENT FOR INITIAL CURE OF POLYESTER PLASTIC; AND COMPLETING CURE OF THE RESULTING SPHERICAL DROPS IN A LOWER PART OF THE HEAT-TRANSFER MEDIUM. 